CN101755021A - Adhesion promoting layer for composite assemblies - Google Patents

Adhesion promoting layer for composite assemblies Download PDF

Info

Publication number
CN101755021A
CN101755021A CN200780100003A CN200780100003A CN101755021A CN 101755021 A CN101755021 A CN 101755021A CN 200780100003 A CN200780100003 A CN 200780100003A CN 200780100003 A CN200780100003 A CN 200780100003A CN 101755021 A CN101755021 A CN 101755021A
Authority
CN
China
Prior art keywords
adhesion promoting
promoting layer
prepreg
resin
base material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN200780100003A
Other languages
Chinese (zh)
Other versions
CN101755021B (en
Inventor
克里斯·哈林顿
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hexcel Composites Ltd
Original Assignee
Hexcel Composites Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hexcel Composites Ltd filed Critical Hexcel Composites Ltd
Publication of CN101755021A publication Critical patent/CN101755021A/en
Application granted granted Critical
Publication of CN101755021B publication Critical patent/CN101755021B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/242—Applying crosslinking or accelerating agent onto compounding ingredients such as fillers, reinforcements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/249933—Fiber embedded in or on the surface of a natural or synthetic rubber matrix
    • Y10T428/249939—Two or more layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer

Abstract

The adhesion between an underlying composite material and its surface finish is increased by including an adhesion promoting layer at the interface where the uncured composite material and the surface finish meet during the lay up of the uncured composite assembly. The adhesion promoting layer includes a cure accelerating agent for the composite material matrix resin.

Description

The adhesion promoting layer of composite assemblies
Background of invention
1. invention field
The present invention relates in general to and is used for matrix material and the method that each layer with composite assemblies combines.More specifically, the present invention relates to promote adhere between the external portion of the structure division of composite assemblies and described assembly, no matter this external portion is gel coat coating (gel coating) or other base material.
2. the explanation of prior art
Matrix material comprises the combination of resinous substrates and fiber reinforced material.Matrix material has been developed and has been used for various application, comprises a large amount of resin/fiber combinations and orientation.The composite assemblies of common type comprises the infrastructure composite assemblies that is coated with surface daub on a wall thing (surface finish).Construction package generally includes resinous substrates, and wherein multilayer (synusia) fiber reinforced material is arranged in this resinous substrates.The surface daub on a wall thing comprises various resin coatings, foam, timber, metal and plastic layer zoarium.
The matrix material of preimpregnation (prepreg) is widely used in the manufacturing composite component.Prepreg is the combination of uncured resinous substrates and fiber reinforced material, and it is in the form of carrying out molding and being solidified into the resulting composite parts prepared.By steeping fiber reinforced material with resin prepreg, manufacturers can control the amount and the position of the resin that is impregnated into fibre network carefully, guarantees that resin is distributed in the network as required.Well-known is that the distribution in fibre network of the relative quantity of fiber and resin and resin has bigger influence to the structural performance of parts in the composite component.Prepreg is the preferred material that is used for the manufacturing structure parts, and importantly, these parts satisfy the intensity and the weight requirement of having set up.
Gel coating is the surface coated technology of using always, wherein usually resin is applied to die surface and is partially cured to gelatinized.Then resin and fiber upholder are laminated on the gel coat coating or as prepreg and use.Then resulting assembly is solidify to form composite component.The gel coat coating has been widely used in shipping industry, is used to make big parts such as hull and mast and requires smooth and uneven surface to be coated with other ship components of jewelry.The gel coat coating also has been used to make other big parts, and for example big size, high strength and low weight are the wind turbine blades (wind turbine blade) of expectation combination.
The resinous substrates that is generally used for above-mentioned big structure is formulated as in about 120 ℃ temperature-curable.These resins are often used with the form of prepreg, and described prepreg comprises about 60～70wt% fortifying fibre such as glass fibre or carbon fiber and about 30～40wt% thermoset resin substrate such as Resins, epoxy.Along with part dimension increases, solidification value becomes important consideration.Need lot of energy, structure has cost desired high-temperature behavior and enough big baker and does not have economic attractiveness.In addition, be used for to make by the precious materials of costliness, will become extremely expensive along with the part dimension for the treatment of molding increases this at 120 ℃ of workpiece (tooling) that reach higher solidification value molding composite parts.
A kind of method that reduces big parts molding cost once moved to solidification value and was lower than 100 ℃.The target solidification value that is lower than 90 ℃ has been attractive especially.For hull and other big structure, attempted maximum solidification value in about 65 ℃ and lower magnitude.Regrettably, the reduction of solidification value also causes the binding property between gel coat coating and the bottom matrix material to descend, no matter how long the assembly solidified time has.
A kind of gel coat coating that improves once was the hardener dose that improves in the resinous substrates of uncured matrix material in the fusible method of low solidification value.This method provides fusible and has improved to a certain degree.But when adding extra solidifying agent, the room temperature treatment time of resin or prepreg (being also referred to as the external time (out-life)) sharply descends.In addition, when using extra solidifying agent, the viscosity of resin or prepreg (tackiness) descends quickly.In order to make the gel coat coating of uncured matrix material when assembly forms and in the mould and the adhesion of other laminate, need good viscosity.
Another improves gel coat coating and relates between matrix material (prepreg) and gel coat coating in the fusible method of low solidification value tackiness agent is set.These binder layers are also referred to as " tack coat ", are made of two portions usually.First part at the surface spreading of gel coat coating, adds second section afterwards soon with the mould of matrix material (prepreg) laying in gel coating after the gelling of gel coat coating.This method is not entirely satisfactory, because be difficult to use the flat coating of two kinds of tackiness agent parts.In addition, there is environmental concerns, for example has amine corrosion and amine susceptibility moisture/carbonic acid gas for gel coat coating based on Resins, epoxy; For polyester gel coat coating system, there are vinylbenzene discharging misgivings.
In sum, exist to be used for preparing the technology of composite assemblies and the lasting demand of system in low solidification value for exploitation, the binding property between bottom matrix material and the external facing in this composite assemblies (exteriorfinish coating) improves.
Summary of the invention
Even, be used to improve fusible method and system between matrix material and their external facing according to the invention provides when described matrix material during in lower temperature-curable.
The present invention's part is based on such discovery, promptly can improve the binding property between bottom matrix material and its surface daub on a wall thing by in the process of the uncured composite assemblies of laying, comprising adhesion promoting layer at the interface what uncured matrix material and surface daub on a wall thing met.Find that further this fusible raising can obtain under the situation of external time of significantly not reducing uncured matrix material or viscosity.In addition, find that this fusible raising is suitable for improving the binding property between the temperature that is lower than 100 ℃ (preferably 60 ℃ to 90 ℃ temperature) solidified matrix material and gel coat coating system especially well.
The present invention includes and be used for two surface bonding method together, the matrix material that wherein has first surface combines with the base material with second surface.Described matrix material comprises uncured thermosetting resin, one or more are used for the solidifying agent and the fiber reinforced material of described thermosetting resin.When during combination matrix material and surface substrate being put together, first surface and second surface form bonding interface.As feature of the present invention, adhesion promoting layer is set to improve binding property at bonding interface.Described adhesion promoting layer comprises the curing catalyst that is used for described uncured thermosetting resin.
The present invention also comprises the composite component of using described adhesion promoting layer to make, and the uncured prepreg that comprises adhesion promoting layer.Described adhesion promoting layer can use with the prepreg type of broad variety, and described prepreg type comprises prepreg and contains (fully formulated) matrix resin of preparation fully or (partially formulated) matrix resin of part preparation (it only becomes preparation fully during curing process).The present invention is suitable for preparing big composite component particularly well, and alap solidification value is kept in described composite component expectation, still keeps the binding property of the proper level between matrix material and the surface substrate simultaneously.
With reference to following detailed description also in conjunction with the accompanying drawings, will understand above-mentioned and many further features of the present invention better and follow advantage.
Brief description of drawings
Fig. 1 is the synoptic diagram that makes matrix material and base material bonded illustrative methods, wherein provides adhesion promoting layer conduct according to the present invention at the individual course (separate layer) that is located in during the combined process between matrix material and the base material.
Fig. 2 is the synoptic diagram of alternate exemplary embodiments of the present invention, and wherein adhesion promoting layer is applied to the surface of prepreg, and described prepreg comprises the complete matrix prepared resin that is distributed in whole fiber reinforced material.
Fig. 3 is the synoptic diagram of another alternate exemplary embodiments of the present invention, and wherein said adhesion promoting layer is positioned at the surface of prepreg, and described prepreg comprises the part matrix prepared resin that is positioned on face of fiber reinforced material.Described fiber reinforced material is mounted with solidifying agent, described solidifying agent during curing move through fiber reinforced material along with it and and mixed with resin, thereby the resin of preparation is provided fully.
Detailed Description Of The Invention
The present invention can be used to make the composite assemblies of wide range of types.It is preferred for making big parts for example hull, mast bar and wind turbine blade.Except shipping industry and wind turbine industry, the present invention is used to expect to improve the fusible any field between bottom matrix material and the surface substrate.Preferably, the present invention is used to improve prepreg or other matrix material and also contains the surface daub on a wall thing of resin such as the binding property of gel coat coating.But, the present invention also can be used to improve the binding property of matrix material and various other surface daub on a wall thing (comprising foam, timber, metal and plastic layer zoarium).
The present invention's part is based on such discovery, promptly can improve the binding property between bottom matrix material and its surface daub on a wall thing by in the process of the uncured composite assemblies of laying, comprising adhesion promoting layer at the interface what uncured matrix material and surface daub on a wall thing met.Find that further this fusible raising can obtain under the situation of external time of significantly not reducing uncured matrix material or viscosity.In addition, find that this fusible raising is suitable for improving the binding property between the temperature that is lower than 100 ℃ (preferably 60 ℃ to 90 ℃ temperature) solidified matrix material and gel coat coating system especially well.
The invention is intended to use with existing epoxy prepreg and gel coat coating system, wherein said prepreg comprises complete matrix prepared resin.Term " preparation fully " is meant that matrix resin comprises the solidifying agent of normal amount and other composition that uses during 100 ℃ and higher temperature-curable when prepreg.Adhesion promoting layer of the present invention is designed to only provide at the bonding interface place curing catalyst of additional quantity.Find that even when the lesser temps curing of this system at 60 ℃～90 ℃, prepreg/gel coat coating interface place comprises curing catalyst makes bonding strength obviously improve.
As an example, adhesion promoting layer according to the present invention is shown in 10 among Fig. 1.Described adhesion promoting layer 10 is used to improve the binding property between base material such as gel coat coating 12 and matrix material such as the prepreg 14.Well-known, originally described gel coat coating 12 is applied to mould 16 and partly solidified, thereby forms the agglomerative base material.Gel coat coating 12 can use any gel coat coated material and the gelatinizing process that are used to prepare the composite structure body to form.Described gel coat coating should be the agglomerative state before contact adhesion promoting layer 10.The gel coat coating of using Resins, epoxy to make is preferred.Other gel coat coating resin that is fit to comprises polyester, vinyl ester resin, urethane and resole (phenolic resole resin).The gel coat coated material can derive from various commercial source.Example has
Figure GPA00001008557500041
The gel coat coated material derives from HexcelComposites, and Ltd. (Duxford, England).
Prepreg 14 can be any prepreg material that is generally used for preparing big structure.Prepreg 14 comprises uncured thermosetting resin, solidifying agent and/or additive and fiber reinforced material.As mentioned above, select uncured thermosetting resin, solidifying agent and/or additive, thereby, provide the resinous substrates of preparation fully according to the practice that is used for concrete prepreg system of having set up.Described fiber reinforced material can be made by any fiber type that is used to prepare matrix material, and described fiber type comprises common glass fibre, carbon fiber, ceramic fiber, Kevlar (aromatic polyamide), right-Kevlar (p-aramid), silica fiber, thermoplastic material fiber, boron fibre, ceramic fiber and natural fiber.These fibers can be that cut off, that break, randomly-oriented, one-way orientation or be made into fabric.Preferred glass fibers and carbon fiber.Fiber reinforced material can be for being used to prepare any form of composite structure body.These forms comprise Woven fabric, unidirectional fibre, the quasi-isotropic and randomly-oriented fiber that can be cut off or break.Fiber reinforced material can be single or multiple lift.According to concrete application, the weight of the number of monofilament and fiber reinforced material also can vary widely in each fiber yarn.For big structure, fiber reinforced material should have the weight at 40 to 4000 gram/square metre (gsm) orders of magnitude.Optimum fiber strongthener weight is 150～2500gsm, and special preferred weight is at the order of magnitude of 300～1500gsm.The number of the monofilament of every fiber also can vary widely, and can be 3000 to 320,000 the order of magnitude usually.For fiber reinforced material based on carbon, preferred 3,000～160,000 monofilament of every fiber, preferred especially 3,000～40,000 spy (tex).For glass fibre reinforcement, the fiber with 300～2400 spies/fiber is preferred for making big structure.
Shown exemplary prepreg 14 thorough impregnations have the solidifying agent (one or more) of uncured thermosetting resin and appropriate amount and the uniform mixture of additive (if any), thereby the resin of preparation fully is provided.Resin is formulated as in about 75 ℃～160 ℃ conventional solidification value curing.Can use any resin of preparation fully that is used to prepare the prepreg that is suitable for making big structure.The amount of uncured thermosetting resin should be about 30～60wt% of prepreg gross weight in the prepreg 14, is preferably about 35～45wt%.Comprising fully, the exemplary prepreg of the epoxy substrate resin of preparation comprises
Figure GPA00001008557500051
M9.1 and M9.6, derive from Hexcel Composites (Duxford, England).
The exemplary thermoset resins that can be used for prepreg matrix comprises Resins, epoxy, polyester, vinyl ester resin, resol, cyanate ester resin, bimaleimide resin and benzoxazine colophony.The preferred Resins, epoxy that uses.If desired, can be epoxy resin toughened with thermoplastic material.Uncured resin comprises proper curing agents and is fit to other additive of used concrete resin.Resins, epoxy can be made of separately the bifunctional epoxy resin, perhaps constituting by bifunctional epoxy resin and multifunctional (that is, trifunctional and/or four senses) Resins, epoxy.As an example, the bifunctional epoxy resin comprises based on those of following material: Bisphenol F, (optional bromination) dihydroxyphenyl propane, the diglycidyl ether of phenol-linear phenolic aldehyde epoxy and cresols-linear phenolic aldehyde epoxy, the glycidyl ether of phenol-aldehyde adducts, the glycidyl ether of aliphatic diol, diglycidyl ether, the glycol ether diglycidyl ether, Epikote, Epon, aromatic epoxy resin, aliphatic triglycidyl group ether, the many glycidyl ethers of aliphatic series, epoxidised alkene, brominated resins, aromatics glycidyl group amine, heterocyclic glycidyl imide (glycidylimidine) and acid amides, glycidyl ether, fluorinated epoxy resin, perhaps their arbitrary combination.This bifunctional epoxy resin is preferably selected from diglycidyl ether, the diglycidyl ether of dihydroxyphenyl propane, the diglycidyl dihydroxy naphthlene of Bisphenol F, or their any combination.Most preferred is the diglycidyl ether of dihydroxyphenyl propane or F.This bifunctional epoxy resin can use individually or in the mode of any suitable combination.
Optional polyfunctional epoxy resin can be (cylcoaliphatic), an alicyclic or heterocycle family saturated, undersaturated, cyclic aliphatic.As an example, other polyfunctional epoxy resin that is fit to comprises based on those of following material: (optional bromination) dihydroxyphenyl propane, phenol-linear phenolic aldehyde epoxy and cresols-linear phenolic aldehyde epoxy, the glycidyl ether of phenol-aldehyde adducts, the glycidyl ether of aliphatic diol, diglycidyl ether, glycol ether diglycidyl ether, Epikote, Epon, aromatic epoxy resin, aliphatic triglycidyl group ether, the many glycidyl ethers of aliphatic series, epoxidised alkene, brominated resins, aromatics glycidyl group amine, heterocyclic glycidyl imide and acid amides, glycidyl ether, fluorinated epoxy resin, perhaps their arbitrary combination.
Described prepreg matrix resin comprises at least a solidifying agent.Can use any solidifying agent that is fit to the cured thermoset resin.Solidifying agent (one or more) can be any solidifying agent that uses with aathermoset resin system usually.The solidifying agent that is fit to comprises aliphatic series and/or aromatic amine, polyetheramine, tertiary amine, cycloaliphatic amines, polymeric amide, amido amine (amidoamine), imidazoles, boron trifluoride, boron trifluoride-amine complex, acid anhydrides and Dyhard RU 100.Specific examples comprises diethylenetriamine (DETA), Triethylenetetramine (TETA) (TETA), tetren (TEPA), m-xylene diamine (MXDA), isophorone diamine (IDPA) and methylene radical-two (hexahydroaniline), and (methylene-di (cyclohexaylamine) (PACM).
Dyhard RU 100 is preferred solidifying agent.Dyhard RU 100 is widely used as epoxy hardener, because it provides room temperature stability and very fast at hot setting.Such as the solidifying agent of Dyhard RU 100 etc. usually and one or more other solidifying agent and/or promotor be used in combination.The suitable combination of solidifying agent comprises: Dyhard RU 100 and 2-phenyl-imidazoles (2PZ); Dyhard RU 100 and N, N-(the 4-methyl--phenylene two (N ', N '-dimethyl urea) (UR500), Dyhard RU 100 and N, N-dimethyl, N '-3,4-dichlorophenyl urea (Diuron).The promotor of example comprises the urea of replacement or the imidazoles of replacement.Preferred promotor comprises N, the N-dimethyl, N '-3,4-dichlorophenyl urea (Diuron), N, the N-dimethyl, N '-3-chloro-phenyl-urea (Monuron) and N, N-(the 4-methyl--phenylene two [N ', N '-dimethyl urea) (UR500).
Matrix resin also can comprise being included in the resinous substrates as performance and strengthens or any other composition of properties-correcting agent.Example has tenderizer (flexibilizer), toughner, thermoplastic core shell particles, fire retardant, wetting agent, pigment and dyestuff, ultraviolet absorbers, antifungal compound, filler and viscosity modifier.
Preferred exemplary substrates resin can comprise: 70～95wt% bisphenol a resin; 1～10wt% Dyhard RU 100; 1-10wt% urea ketone (urone) and 1-10wt%2PZ.More preferably, resin contains: 85～90wt% bisphenol a resin; 3～6wt% Dyhard RU 100; 3～6wt% urea ketone and 3-6wt%2PZ.
Adhesion promoting layer 10 preferably provides with the form of the fibre element (fibrouselement) that is coated with suitable curing catalyst.Fibre element is preferably made by the combination of synthetic or natural fiber or synthon and natural fiber.Suitable fiber comprises glass, carbon, aromatic poly, nylon, polyester, cotton, hemp (hemp) and mestha (kenaf).Glass is preferred fiber type.Fibre element can contain the combination of continuous fibre or discontinuous fibre or continuous fibre and discontinuous fibre.Fibre element can be any form in the known broad form of textile industry.These forms comprise clad can felt (veil), fibrous reticulum (fleece), felt (mat), scrim (scrim), gauze (gauze), non-woven felt and cloth or two-dimensional woven.The face weight of fibre element (areal weight) is 10～1000 gram/square metre (gsm).Preferably, the face weight of fibre element can be 20～600gsm.More preferably, the face weight of fibre element is 40～100gsm.
Described curing catalyst can be catalyzer or the promotor that is suitable for thermosetting resin (particularly Resins, epoxy).Suitable curing catalyst comprises the salt of alkaline-earth metal, the amine salt of trinitride, urea, radical initiator and boron halide complex.The curing catalyst of example comprises: 2-ethyl-4-methylimidazole (2E4MZ); 2-phenyl-imidazoles (2PZ) and Curezol MZ azine S (Curezol MZ azine S).
Preferably, the reactivity of curing catalyst and thermosetting resin is than curing/promotor (one or more) height in the matrix resin Already in.For example, as Dyhard RU 100 and/or 2PZ during as solidifying agent (one or more), preferably curing catalyst is reactive high imidazoles, for example 2-ethyl-4-methylimidazole.
The amount that curing catalyst exists in the adhesion promoting layer can change, and condition is that this amount is enough to promote high chemical conversion degree in the fusible harsh zone of needs.These high degree of conversion are essential for the enough binding propertys with base material.High chemical conversion degree is meant that the most of reaction site (that is, at least 90%) in thermosetting resin and the solidifying agent (one or more) consume.The amount of required curing catalyst is non-stoichiometric amount (non-stoichiometric amount), is preferably determined by employed concrete resinous substrates experience.Preferred amount is a minimum of guaranteeing the required curing catalyst of good binding between matrix material and gel coat coating or other base material.For most of epoxy substrate resins, the amount that is present in the curing catalyst in the adhesion promoting layer should be 1～50gsm.The preferred amounts of curing catalyst is 1～10gsm.
Can use any routine techniques that is used for to filamentary material interpolation chemical composition to make curing catalyst be deposited on fibre element.Curing catalyst can only be applied to fibre element the surface or can thorough impregnation.Preferably curing catalyst is dissolved in the suitable solvent, is applied to fibre element then.The solution that contains curing catalyst can be sprayed onto this element, perhaps this element can be dipped in this solution.The application technique of these types is known.
In many situations, expectation provides the adhesion promoting layer with some intrinsic tackinesss (being commonly referred to " viscosity ").Described adhesion promoting layer preferably has enough tackinesss or viscosity, makes the mould that it can stick at the mould of vertical orientation or have complicated shape.According to the present invention, discovery can be incorporated into tackifier (tackagent) and provide viscosity in the adhesion promoting layer and can not influence integrated bond between base material and the prepreg nocuously.
Tackifier are any compounds of tackifying, and it is known that itself and thermosetting resin are used in combination.Can be incorporated into acrylonitrile-butadiene liquid rubber that suitable tackifier in the adhesion promoting layer comprise carboxy blocking for example Hycar CTBN 1300X8 and Hycar CTBN 1300X13 (Noveon, be positioned at Cleveland, and the end capped acrylonitrile-butadiene liquid rubber of amine such as Hycar ATBN1300X16 and Hycar 1300X21 (also deriving from Noveon) OH).Other suitable tackifier comprise the product (being commonly referred to adducts) of the chemical reaction between these rubber and the Resins, epoxy, Hypox RA1340 or Hypox RA 840 (CVC Specialty Chemicals for example, be positioned at Moorestown, NJ), and alternative for example Struktol Polydis 3614 (Schill and Seilacher, be positioned at Hamburg, Germany).Carboxylated nitrile elastomerics for example Nipol 1472 (Zeon corporation, Tokyo Japan) are the tackifier of example.Polyurethane prepolymer toughner for example RAM 965 (Huntsman is positioned at Salt Lake City, UT) also is the tackifier of example.
Tackifier be preferably dissolved in curing catalyst institute dissolved same solution in, make two kinds of components be applied to fibre element simultaneously.But, if desired, tackifier can be applied to fibre element separately.When adhesion promoting layer comprises tackifier, preferably reduce the amount of curing catalyst, make the total amount of curing catalyst and tackifier be no more than 50gsm.But if desired, the total amount of curing catalyst and tackifier can be higher.
When using, the amount of tackifier should be 5～50wt% of curing catalyst and tackifier gross weight.Preferably, the amount of tackifier can be 10～40wt% of curing catalyst and tackifier gross weight, even 15～35wt% more preferably.Keep being adhered to the mould that is in required orientation in order to ensure adhesion promoting layer, can be according to the amount of used concrete tackifier and needed viscosity amount change tackifier.
Alternative example embodiment of the present invention as shown in Figure 2.In this embodiment, adhesion promoting layer 20 is attached on the prepreg 24, follows prepreg 24 layings to the gel coat coating 22 that is positioned on the mould 26.Prepreg 24 comprises the uncured resin matrix of preparation fully.This embodiment has been simplified the use of adhesion promoting layer, because adhesion promoting layer preferably is added into prepreg during the prepreg manufacturing process.This has eliminated the demand that must individually adhesion promoting layer be applied to the gel coat coating during moulding technology.In this embodiment, preferably, curing catalyst is positioned at the surface 28 of adhesion promoting layer 20.This structure has prevented or has at least significantly reduced prepreg 24 layings any contact between curing catalyst and the resinous substrates in mould and before solidifying.By preventing contacting between active higher curing catalyst and the uncured resin matrix, improved the external time that prepreg/adhesion promoting layer makes up (24 and 20).
Another example embodiment of the present invention as shown in Figure 3.In this embodiment, adhesion promoting layer 30 also is attached on the prepreg 34, follows prepreg 34 layings to the gel coat coating 32 that is positioned on the mould 36.Preferably in the process of making prepreg, adhesion promoting layer 30 is attached on the prepreg 34.Prepreg 34 does not contain complete matrix prepared resin.The substitute is, prepreg 34 is divided into and contains the fibrolaminar prepreg assembly 35 that is impregnated with part matrix prepared resin.This part matrix prepared resin lacks some or all necessary solidifying agent of normal cured resin (one or more).The solidifying agent (one or more) that is lacked is positioned at the pars fibrosa 37 of prepreg.Solidifying agent (one or more) can this pars fibrosa 37 of thorough impregnation, and perhaps they can be provided with away from the prepreg assembly 35 that contains matrix resin.In every kind of situation, by pars fibrosa 37, resin and solidifying agent (one or more) just mix up to resin transfer during curing process.Along with resin transfer during curing process by pars fibrosa 37, this part matrix prepared resin becomes preparation fully.Therefore, the curing catalyst that is present in adhesion promoting layer 30 is just to contact with matrix resin when preparing fully up to matrix resin.The prepreg that becomes complete matrix prepared resin at the matrix resin of solidification process middle part assignment system is described in EP 1553125A1, and it incorporates its content into the application as a reference corresponding to U.S. Patent application 11/031,190.
Each embodiment of following enforcement:
Embodiment 1
By (Shikoku ChemicalCorporation-Chiba, Japan) methylethylketone (MEK) that is dissolved in 1500g makes the solution of curing catalyst with the 2-ethyl-4-methylimidazole (2E4MZ) of 50g.The Oracet that comprises 0.1g is red, and (Ciba Specialty Chemicals-Basel is Switzerland) as the dyestuff of differentiating that purpose is used.The face weight of making is that (model S5030 derives from Johns Manville, and Waterville is Ohio) by this solution, and dry 2 hours of ambient temperature air for the non-woven glass felt of 50gsm.Resulting adhesion promoting layer is that face weight is the felt of 53.4gsm.As reference, this felt also immerses MEK and carries out drying.The face weight of this felt is 50.2gsm.Therefore, the felt that is used as adhesion promoting layer is absorbed with the imidazoles of about 3.2gsm, and it accounts for about 6% of adhesion promoting layer gross weight.This material is designated as APL1.
Will
Figure GPA00001008557500101
02 (deriving from Hexcel Composites Ltd, Duxford, the commercially available gel coating of UK) was applied to composite material work piece (composite tool), 70 ℃ of gellings 30 minutes.Prepared APL 1 felt is applied to the part of gel coat coatingsurface.Stay some gel coat coatings and do not cover APL 1 felt.With the described same way as of Fig. 1 three layers of prepreg are laid on APL 1 felt or the gel coat coating, this prepreg contains the 38wt%M9.6 matrix resin that is impregnated into LBB 1200 glass fabrics.M9.6 is the Resins, epoxy of preparing fully, contains Dyhard RU 100 and urea ketone as solidifying agent.M9.6 derive from Hexcel Composites Ltd. (Duxford, UK).LBB1200 is 0 ° /+45 °/-45 ° three axial glass fabric (triax glass fabric) with 1200gsm fibrous face weight, derive from HexcelReinforcements (Villeurbanne, France).
This assembly is sealed with vacuum bag, use following cure cycle to be cured: 1) from envrionment temperature; 2) heat-up rate with 1 ℃/min is elevated to 80 ℃; 3) stopped 4 hours; Then 4) be cooled to envrionment temperature.This vacuum solidification technical description is in deriving from Hexcel Composites Ltd, Duxford, " prepreg technical manual (the Prepreg Technology Handbook) " of UK.In order to carry out other comparison, the sample administration of prepreg to the gel coat coating that does not have APL 1 felt, and is cured in the mode identical with other sample, difference is that the target solidification value is 120 ℃.
For the evaluate cure laminate in conjunction with integrity, the cured layer zoarium is separated, and the zone in conjunction with difference of check cutting edge.The band saw (band saw) that use is equipped with the coarse cutting edge (gullotted rough cutblade) of spline carries out this to be cut apart.The blade of the type lacks most blade, and this produces very irregular and coarse side cut.The every 2cm of the blade of the saw of this spline has about 1 tooth, and wherein each tooth is that 10mm is long, then is the teeth groove (gap) of about 10mm.Tip/the edge of this blade has the diamond coatings that applies the wearing and tearing/cutting that is used for optimum.Carrying out this cutting makes blade at last by the gel coat coating.After blade leaves the gel coat coating, in the 5mm of blade both sides, there be not upholder.
In the part of not using felt, large stretch of gel coat coating (about 1cm 2) removed by the surface of sawing process from laminate.This part gives bonding grade 3 (referring to table 1).In the place of using adhesion promoting layer, produce the otch of clean (clean), and do not have the gel coat coating layer portion to be removed.This part gives bonding class 4.Also obtain bonding class 4 at much higher standard solidification value (120 ℃) solidified sample.This embodiment confirms, when according to the present invention when 80 ℃ low solidification value is used adhesion promoting layer, obtain the binding property of improving between prepreg and the gel coat coating.
Embodiment 2
Will
Figure GPA00001008557500111
02 gel coat coating is applied to composite material work piece, solidifies 30 minutes at 70 ℃.Prepared APL 1 felt is applied to the part of gel coat coatingsurface, keeps some gel coat coatingsurfaces and do not cover APL 1 felt.As shown in Figure 1, will be referred to as three layers of prepreg types of material laying of D1 on APL 1 felt or gel coat coating.This assembly is sealed with vacuum bag, use following cure cycle to be cured: 1) from envrionment temperature; 2) heat-up rate with 1 ℃/min is elevated to 80 ℃; 3) stopped 2 hours; With 4) be cooled to envrionment temperature.This D1 prepreg is a type shown in Figure 3, and wherein the resin molding of part preparation is arranged in a part 35 of prepreg, and residue solidifying agent (one or more) is arranged in the another part 37 that contains fiber reinforced material.The prepreg of the type also is illustrated among the embodiment 2 of european patent application 1553125A1.
The resin molding of this part preparation comprises: (both all derive from Huntsman Advance Materials (Duxford, UK)), 4.0wt%DYHARD 100SH and 5.0wt%UR500 for 43.5wt%GY280 Resins, epoxy and 43.5wt%GT7071 Resins, epoxy.DYHARD 100SH is micronized Dyhard RU 100, and UR500 is a urea ketone solidifying agent, all derive from Deugussa (Zurich, Switzerland).Fiber reinforced material is and embodiment 1 employed (that is, LBB 1200) mutually in specie, and difference is that it is loaded with the 2PZ of the 4wt% of the resin that enough formations prepare fully, rather than is loaded with the resin of preparation fully.In case load after the 2PZ, fiber reinforced material just slightly is adhered to the resin molding of part preparation, thereby the final prepreg assembly shown among Fig. 3 34 is provided.It should be noted, aforementioned weight percentage with the resin transfer of part preparation to contact with 2PZ solidifying agent in the fiber reinforced material and mix with it after the resin prepared fully be benchmark.Enough providing the nominal resin content with the amount of the part matrix prepared resin molding of fiber reinforced material adhesion is the whole prepreg 34 of 38wt%.
Though in embodiment 2 and 3, use the blend of two kinds of Resins, epoxy, can also adopt liquid resin component more or less, this selection is well known to a person skilled in the art.In this embodiment, routine as shown in Figure 1, adhesion promoting layer (APL 1) is applied directly to the gel coat coating.But, can in manufacturing processed or during other, adhesion promoting layer be adhered to fiber reinforced material, thereby the assembly of type shown in Figure 3 is provided, wherein prepreg and adhesion promoting layer are applied to the gel coat coating simultaneously.
In the identical mode of embodiment 1, use coarse blade on band saw, the gained laminate to be cut.In the part of not using APL 1 felt, the order of magnitude is 1cm 2Large stretch of gel coat coating removed by the surface of sawing process from laminate.This part gives bonding grade 3 (referring to table 1).Place using the APL1 felt produces clean otch, and does not have the part of gel coat coating to be removed.This part gives bonding class 4.This embodiment also confirms, when according to the present invention when 80 ℃ low solidification value is used adhesion promoting layer, improved the binding property between prepreg and the gel coat coating.
Embodiment 3
Will
Figure GPA00001008557500121
02 was applied to composite material work piece, 70 ℃ of gellings 30 minutes.Prepared APL 1 felt is applied to the part of gel coat coatingsurface.The felt (felt that does not contain CAA) that does not flood curing catalyst is applied to second section.Keep some gel coat coatings and do not cover this two kinds of felts.Mode with identical with embodiment 1 will be referred to as six layers of prepreg types of material laying of D2 on APL1 felt, the felt that does not contain CAA or gel coat coating.This assembly is sealed with vacuum bag, use following cure cycle to be cured: 1) from envrionment temperature; 2) heat-up rate with 1 ℃/min is elevated to 65 ℃; 3) stopped 16 hours; With 4) be cooled to envrionment temperature.
The D2 prepreg is identical with the D1 prepreg, and difference is to change a little the ratio of Resins, epoxy, and to improve the viscosity of prepreg, this is adjusted in the industry is known.In addition, the fiber reinforced material that is used for the resin of part preparation is changed into BB600, and it is+and 45 °/-45 ° twin shafts are to glass fabric, have 600gsm fibrous face weight, also derive from Hexcel Reinforcements.BB600 is loaded with the 2E4MZ of the 4wt% of the resin that enough formations prepare fully.In case load after the 2E4MZ, fiber reinforced material just slightly is adhered to resin molding.All the percentage ratio of prepreg assembly (that is, being impregnated with the BB600 and the unidirectional fibre that is loaded with 2PZ of the resin of part preparation) mesostroma resin is nominal 38wt%.
In the identical mode of embodiment 1, use coarse blade on band saw, the gained laminate to be cut.In the part that does not have felt, the order of magnitude is 1cm 2Large stretch of gel coat coating removed by the surface of sawing process from laminate.This part gives bonding grade 3.In the place that has the felt that does not contain CAA, the order of magnitude is 2cm 2Large stretch of gel coat coating removed by the surface of sawing process from laminate.This part gives bonding grade 2.Use the place of flooding felt, produce clean otch, and do not have the part of gel coat coating to be removed basically.This part gives bonding class 4.This embodiment further confirms, when according to the present invention when 65 ℃ low solidification value is used adhesion promoting layer, improved the binding property between prepreg and the gel coat coating.
Table 1
Bonding grade Explanation
??0 No bounding force-gel coat coating is peeled off on a sheet material
??1 Minimum bounding force-in coarse cutting process, produce big sheet (greater than 2 * 2cm)
??2 The little sheet of slight bounding force-in coarse cutting process, produce (1 * 1cm to 2 * 2cm)
??3 Medium bounding force-in coarse cutting process, produce very little sheet (less than 1 * 1cm)
??4 Good bounding force-in coarse cutting process, do not produce basically sheet
Following table 2 has been summed up the result of embodiment 1-3, demonstration uses adhesion promoting layer (APL1) to improve binding property for the prepreg system of the dipping wholly or in part of the Resins, epoxy that comprises wholly or in part preparation, and is presented at the binding property that 65-105 ℃ solidification value provides this improvement.In addition, this fusible improvement is to realize under the situation of the external time of not damaging prepreg.
Table 2
Material Solidification value (℃) In the external time of room temperature (about 23 ℃), day Bonding grade
M9.6-does not have APL 1 120 (standards) ??42 ??4
M9.6-does not have APL 1 ??80-105 ??42 ??2
??M9.6+APL?1 ??80 ??42 ??4
??D1 ??80 ??＞250 ??3
??D1+APL?1 ??80 ??＞250 ??4
??D2 ??65 ??＞250 ??3
Material Solidification value (℃) In the external time of room temperature (about 23 ℃), day Bonding grade
D2+ does not contain the felt of CAA ??65 ??＞250 ??2
??D2+APL?1 ??65 ??＞250 ??4
Embodiment 4
Be prepared as follows solution: with Hypox RA-95 (the CVC speciality chemicals Inc of 15g, Moorestown, NJ, USA) and the 2-ethyl-4-methylimidazole of 85g (2E4MZ) (ShikokuChemical Corporation-Chiba Japan) is dissolved in the methylethylketone (MEK) of 900g.This provides the solution that contains 8.5wt%2E4MZ and 1.5wt%Hypox RA-95.
The face weight of making is that (style title S5030 derives from JohnsManville, and Waterville Ohio) by this solution, carried out dry air 2 hours in envrionment temperature for the non-woven glass felt of 50gsm.The gained adhesion promoting layer is that face weight is the felt of 64.2gsm.Therefore, this felt that is used as adhesion promoting layer obtains the 2E4MZ of about 12.1gsm and the Hypox RA-95 of 2.1gsm, and its sum accounts for 22% of adhesion promoting layer gross weight greatly.This material is called APL 2.
In adhesion test (80 ℃ of curing), APL 2 provides the performance identical with APL1, have in addition enough tackinesss or ' viscosity ', make it be positioned over vertical die location and during being processed into complicated mold shape, help its placement.After room temperature storage 7 days, the viscosity of this material is reduced to 0.
Embodiment 5
Be prepared as follows the solution of solid rubber: with the Nipol 1472 of 25g (Zeon corporation, Tokyo, Japan) and the 2E4MZ of 50g be dissolved among the MEK of 500g.240g gained solution is mixed with other 160g MEK.This provides the MEK solution that contains 5.2wt%2E4MZ and 2.6wt%Nipol 1472.
The face weight of making is that (style title S5030 derives from JohnsManville, and Waterville Ohio) by this solution, carried out dry air 2 hours in envrionment temperature for the non-woven glass felt of 50gsm.The gained adhesion promoting layer is that face weight is the felt of 66.4gsm.Therefore, this felt that is used as adhesion promoting layer obtains the 2E4MZ of about 10.8gsm and the Nipol 1472 of 5.4gsm, and it accounts for 24% of adhesion promoting layer gross weight greatly.This material is called APL 3.
In adhesion test (80 ℃ of curing), APL 3 provides the performance identical with APL1, have in addition enough tackinesss or ' viscosity ', make it be positioned over vertical die location and during being processed into complicated mold shape, help its placement.After room temperature storage 30 days, the viscosity of this material does not change.
Thereby illustrative embodiments of the present invention has been described, those skilled in the art it should be noted that the disclosure of the inside only is exemplary, can carry out various other replacements, variation and modification within the scope of the invention.Therefore, the present invention is not limited by above-mentioned embodiment, and is only limited by claims.

Claims (26)

1. with two surface bonding method together, comprise the steps:
Matrix material with first surface is provided, and described matrix material comprises uncured thermosetting resin, one or more are used for the solidifying agent and the fiber reinforced material of described thermosetting resin;
Base material with second surface is provided;
Described first surface and second surface are put together, thereby form bonding interface, the described interface of adhesion promoting layer between described first surface and second surface wherein, described adhesion promoting layer comprises the curing catalyst that is used for described uncured thermosetting resin; And
Solidify described uncured thermosetting resin.
According to claim 1 with two surface bonding method together, wherein said adhesion promoting layer comprises the fibrous carrier that is used for described curing catalyst.
According to claim 1 with two surface bonding method together, wherein said base material is the gel coat coating.
According to claim 1 with two surface bonding method together, wherein said thermosetting resin is selected from Resins, epoxy, polyester, vinyl ester resin, resol, cyanate ester resin, bimaleimide resin and benzoxazine colophony.
According to claim 4 with two surface bonding method together, wherein said curing catalyst is selected from the amine salt of salt, trinitride, urea, radical initiator and the boron halide complex of imidazoles, alkaline-earth metal.
According to claim 2 with two surface bonding method together, wherein said fiber reinforced material and described fibrous carrier comprise the fiber that is selected from glass fibre, carbon fiber, Kevlar, tynex, trevira, cotton fibre, hemp fibre and kenaf.
According to claim 2 with two surface bonding method together, wherein said matrix material was comprising described adhesion promoting layer before forming described bonding interface between described first surface and the second surface.
According to claim 1 with two surface bonding method together, wherein said uncured thermosetting resin and described solidifying agent mix in described matrix material.
According to claim 1 with two surface bonding method together, wherein said uncured thermosetting resin and at least a described solidifying agent are isolated from each other in described matrix material.
According to claim 7 with two surface bonding method together, wherein said fibrous carrier is that fiber reinforced material is positioned at that part of of described first surface.
11. according to claim 1 with two surface bonding method together, the described thermosetting resin of wherein said curing carries out in the temperature that is lower than 100 ℃.
12. according to claim 1 with two surface bonding method together, wherein said adhesion promoting layer comprises tackifier.
13. a composite component, it comprises matrix material and the base material that has combined according to claim 1.
14. according to the composite component of claim 13, wherein said base material comprises solidified gel coat coating.
15. be used for the prepreg in conjunction with base material, described prepreg comprises:
Matrix material, described matrix material comprise uncured thermosetting resin, one or more are used for the solidifying agent and the fiber reinforced material of described thermosetting resin; And
Adhesion promoting layer, described adhesion promoting layer comprise curing catalyst that is used for described uncured thermosetting resin and the fibrous carrier that is used for described curing catalyst.
16. according to the prepreg in conjunction with base material of being used for of claim 15, wherein said thermosetting resin is selected from Resins, epoxy, polyester, vinyl ester resin, resole, cyanate ester resin, bimaleimide resin and benzoxazine colophony.
17. according to the prepreg in conjunction with base material of being used for of claim 16, wherein said curing catalyst is selected from the amine salt of salt, trinitride, urea, radical initiator and the boron halide complex of imidazoles, alkaline-earth metal.
18. according to the prepreg in conjunction with base material of being used for of claim 15, wherein said fiber reinforced material comprises described fibrous carrier.
19. according to the prepreg in conjunction with base material of being used for of claim 15, wherein at least a described solidifying agent and described uncured thermosetting resin are isolated, and on described uncured thermoplastic resin and the described fiber reinforced material between the described fibrous carrier.
20. according to the prepreg in conjunction with base material of being used for of claim 15, wherein said adhesion promoting layer comprises tackifier.
21. be used to make uncured matrix material and base material bonded adhesion promoting layer, wherein said adhesion promoting layer comprises curing catalyst that is used for described uncured matrix material and the fibrous carrier that is used for described curing catalyst.
22. according to claim 21 be used to make uncured matrix material and base material bonded adhesion promoting layer, the weight of wherein said fibrous carrier be 10～1000 the gram/square metre, in the described adhesion promoting layer consumption of curing catalyst be 1～50 the gram/square metre.
23. according to claim 21 be used to make uncured matrix material and base material bonded adhesion promoting layer, the weight of wherein said fibrous carrier be 20～600 the gram/square metre, in the described adhesion promoting layer consumption of curing catalyst be 1～10 the gram/square metre.
24. according to claim 21 be used to make uncured matrix material and base material bonded adhesion promoting layer, the weight of wherein said fibrous carrier be 40～100 the gram/square metre, in the described adhesion promoting layer consumption of curing catalyst be 1～10 the gram/square metre.
25. according to claim 21 be used to make uncured matrix material and base material bonded adhesion promoting layer, it also comprises tackifier.
26. an assembly, it comprises the prepreg of the claim 15 that combines the gel coat coating.
CN200780100003.0A 2007-05-23 2007-05-23 Adhesion promoting layer for composite assemblies Expired - Fee Related CN101755021B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IB2007/001601 WO2008142474A1 (en) 2007-05-23 2007-05-23 Adhesion promoting layer for composite assemblies

Publications (2)

Publication Number Publication Date
CN101755021A true CN101755021A (en) 2010-06-23
CN101755021B CN101755021B (en) 2014-12-31

Family

ID=38984510

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200780100003.0A Expired - Fee Related CN101755021B (en) 2007-05-23 2007-05-23 Adhesion promoting layer for composite assemblies

Country Status (7)

Country Link
US (1) US9328262B2 (en)
EP (1) EP2148907B1 (en)
CN (1) CN101755021B (en)
AT (1) ATE553167T1 (en)
DK (1) DK2148907T3 (en)
ES (1) ES2385677T3 (en)
WO (1) WO2008142474A1 (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009030221B4 (en) * 2009-06-23 2011-04-14 Benteler Automobiltechnik Gmbh Method for producing a fuel tank
GB201121304D0 (en) * 2011-12-12 2012-01-25 Hexcel Composites Ltd Improved composite materials
EP2794735B1 (en) * 2011-12-22 2019-07-17 Hexcel Holding GmbH Improvements in or relating to fibre reinforced composites
US9365685B2 (en) 2012-02-28 2016-06-14 Ut-Battelle, Llc Method of improving adhesion of carbon fibers with a polymeric matrix
WO2016171060A1 (en) * 2015-04-21 2016-10-27 三菱瓦斯化学株式会社 Fiber-reinforced thermoplastic resin composition
US10597559B2 (en) * 2016-06-06 2020-03-24 Crane Composites, Inc. Method of manufacturing a composite panel containing lauan or other moisture-carrying or moisture-absorbing material using adhesion promoter and panel made using the method
WO2018052707A1 (en) * 2016-09-13 2018-03-22 Dow Global Technologies Llc Catalyst-doped sizing agent for preparation of high areal weight fiber shelf-stable prepreg or molding compound intermediates
US11273622B2 (en) 2016-12-14 2022-03-15 The Boeing Company Stiffening elements that comprise integral current flowpaths
US11014337B2 (en) * 2016-12-14 2021-05-25 The Boeing Company Laminate structures comprising fiber-reinforced thermoplastic prepreg plies
US11077644B2 (en) 2016-12-14 2021-08-03 The Boeing Company Material systems and methods of manufacturing material systems

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4242406A (en) * 1979-04-30 1980-12-30 Ppg Industries, Inc. Fiber reinforced composite structural laminate composed of two layers tied to one another by embedded fibers bridging both layers
DD221419A1 (en) 1984-03-02 1985-04-24 Bernau Schichtpressstoff METHOD FOR THE PRODUCTION OF LAYER PRESSURES OR BZW. BASIC MATERIAL FOR PCB
DE3508601A1 (en) 1985-03-11 1986-09-11 Dynamit Nobel Ag, 5210 Troisdorf Metal foil having an adhesive-agent coating for base materials for printed circuits, and a method for producing the base material
US5164127A (en) * 1990-10-02 1992-11-17 Cook Composites And Polymers Co. Method of preparing molded coatings for gel coated composites
EP0714743A1 (en) * 1994-11-29 1996-06-05 ECP Enichem Polimeri Netherlands B.V. Process for the production of gel-coated articles
ES2171048T3 (en) * 1997-10-10 2002-08-16 Cook Composites & Polymers COMPOSITIONS OF UNSATURATED POLYESTER RESINS, WATER RESISTANT.
TW384299B (en) 1997-11-26 2000-03-11 Sumitomo Bakelite Co Production of prepreg and laminate
CA2332341C (en) 1998-05-20 2005-11-29 Cytec Technology Corp. Manufacture of void-free laminates and use thereof
US6117536A (en) * 1998-09-10 2000-09-12 Ga-Tek Inc. Adhesion promoting layer for use with epoxy prepregs
EP1128958B2 (en) 1998-11-06 2011-08-03 Gurit (UK) Limited Moulding materials
US20030082385A1 (en) * 2001-07-13 2003-05-01 Toray Composites (America), Inc. Quick cure carbon fiber reinforced epoxy resin
GB2409837B (en) 2004-01-10 2006-09-06 Hexcel Composites Ltd Fibre reinforced resin assembly
US20100147451A1 (en) * 2007-04-24 2010-06-17 Evonik Degussa Gmbh Use of silanes as adhesion promoters between two organic surfaces

Also Published As

Publication number Publication date
EP2148907A1 (en) 2010-02-03
WO2008142474A1 (en) 2008-11-27
EP2148907B1 (en) 2012-04-11
ATE553167T1 (en) 2012-04-15
ES2385677T3 (en) 2012-07-30
DK2148907T3 (en) 2012-07-23
US9328262B2 (en) 2016-05-03
CN101755021B (en) 2014-12-31
US20100068497A1 (en) 2010-03-18

Similar Documents

Publication Publication Date Title
CN101755021B (en) Adhesion promoting layer for composite assemblies
JP4141478B2 (en) Epoxy resin composition for fiber reinforced composite materials
CA2650563C (en) Epoxy resin composition for fiber-reinforced composite material
EP2850119B1 (en) Fast cure epoxy resins and prepregs obtained therefrom
JPH05261859A (en) Lightning strike composite and process
US9776341B2 (en) Low density composite materials, their production and use
US8211537B2 (en) Resin composition, and prepreg
CN102869507A (en) Composite material for structural applications
CN108350335A (en) Construction adhesive with improved corrosion resistance
CN104870512A (en) Fast cure epoxy resin systems
JP3958471B2 (en) Epoxy resin composition for self-adhesive surface material and prepreg
WO2015079917A1 (en) Reinforcing fiber fabric substrate, preform, and fiber-reinforced composite material
CN105431287B (en) The improvement of fibre-reinforced composite material or relative improvement
US5512372A (en) Epoxy resin composition and applications, in particular in composite structures, using imidazole/polyamine mixture
KR20190082313A (en) Curable Epoxy / Polyurethane Hybrid Resin System for SMC
CN106170504A (en) The room temperature storage epoxy resin extended
US11377530B2 (en) Toughened adhesive and bonding method using the same
CN107108929B (en) Improved fast curing epoxy resins and prepregs therefrom
JP4141481B2 (en) Epoxy resin composition for fiber reinforced composite materials
JP2013142123A (en) Prepreg, and method for producing prepreg
KR101951632B1 (en) A hybrid prepreg excellent in interfacial adhesion and abrasion resistance and a method for producing the same
US20040039120A1 (en) Process for producing a prepreg resin composition
JP2013142122A (en) Prepreg, and method for producing prepreg
JP4228740B2 (en) Binder composition, reinforced fiber substrate, preform, and method for producing fiber reinforced composite material
CN114008115B (en) Self-adhesive prepreg

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20141231

Termination date: 20210523

CF01 Termination of patent right due to non-payment of annual fee